Stabilized diazo guanidine compound



Patented Jan. 25, 1944 UNITED STATES 2,339,934 STABILIZED DIAZO GUANIDIN E COMPOUND Old Greenwich, and Walter P, Conn., assignors .to American Paul P. McClellan, Ericks, Cos Cob,

Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Original application December 12,

1940, Serial No. plication August 30,

6 Claims.

This invention relates to a new class of chemical compounds, to intermediates and dyes obtained therefrom, and. to their methods of preparation.

The principal object of this invention is to prepare new stabilized diazo compounds, preferably those soluble in water and in the more commonly used organic solvents.

Among the stabilized diazo compounds included herein are, more especially, the reaction products of an ice color diazo component with an alkylol or an alkoxyalkylol derivative of guanidine. Inasmuch as these derivatives each exist in several tautomeric forms, the reaction products prepared from any one may occur as a mixture of isomers which readily undergo rearrangement. Hence, assignment of a definit chemical formula is problematical.

However, the chemical properties of the products and the particular method or methods of preparation disclosed herein cause one of the isomers to appear in excess, and under the present conditions the monomeric form is produced predominantly. Thus the alkylol and alkoxyalkylol guanidine derivatives probably have the formula:

wherein R represents the nucleus of an aromatic amine such as the nucleus of an ice color diazo component; and R2 is an alkylol or alkoxyalkylol group.

These stabilized diazo compounds are resistant to percussion and even when heated in a direct fiame decompose without the hazard of an explosion. When in a dry condition or in an alkaline solution they are stable at temperatures normally encountered throughout all seasons of the year, and hence ma be stored indefinitely. However, these reaction products possess the property of splitting into their original components by treatment with acids at elevated temperatures or with steam containing volatile acid vapors. If this splitting occurs in the presence of an ice color coupling component the regenerated active diazotized component becomes available immediatelyfor reaction with the coupling component and produces the corresponding azo pigment or dye.

To this end it is a further object of this invention to prepare new azo pigments and dyes by mixing an ice color coupling component and the reaction product of an ice color diazo component with an alkylol or alkoxyalkylol derivative of guanidine. As such, the mixture may or may not be colored. However, if a textile material is printed or impregnated with this mixture'and then heated in the presence or an acid, the acid 6. Divided and this ap- 1941, Serial No. 409,059

hydrolyzes the stable diazo compound, splitting it into its components; and the regenerated diazotized component liberated couples with the ice color component to form an azo-pigment or dye..

This acid treatment or ageing as it iscalled, is preferably efiected with a weak acid andat an elevated temperature. Usuallyformicor acetic; acids are used, but various other acids as well as substances liberating acids upon being steamed such as ammonium sulfate, esters of, tartaric,. succinic, etc., acids may be used-particularly when the printed materialis subjected to a subsequent. steam treatment to eife t ageing or develop thecolor. I

Stable alkaline printing pastes can be prepared from the mixture of the ice color coupling component and the reaction product of the ice color diazo component with one of the alkylol oralkoxyalkylol derivatives by dissolving the mixture in a solvent such as water, alcohol, acetone, etc.,. together with various other ingredients such as alkalies', organic bases, impregnating agents,v thickeners such as'starch, gum, etc., well known to those skilled ino the art. Cotton goods can be printed with this paste with the aid of a copper roll. The print is then dried and subsequently the desired color is-developed by. steaming in the presence of acetic acid or other volatile acid vapors. In this manner an insoluble azo pigment is produced in and on the cotton fibers in the form 'of the printed pattern. Such prints are bright and possess remarkable fastness to light and washing.

The facilityv with which the compounds and dyes included in this invention can beused is based upon the. ease with which the stabilized diazamino group present can be split and converted into an active diazo group by heating-in the presence of an acid or an acid liberating substance. This conversion or ageing is usually ef-. fected in a steam chamber and in the presence of a coupling component (e. g. naphthol in the examples given below) to develop or form the color. The following examples describe the preparation of several stabilized diazo compounds included in this invention and further give details as to their use in dyeing and printing textile materials.

EXAMPLE I Monoethylol yuam'dz'ne reacted with p-toluidine diazom'um hydrochloride An aqueous solution of monoethylol guanidine was prepared by introducing 23.4 g. of guanidine carbonate into a dilute sulfuric acid solution. The

p g. of sodium hydroxide dissolved therein. 9.5 g;

of ethylene oxide was added slowly with constant stirring and the temperature maintained at -10 C. After stirring for 12 hours--at- C. a solution containing 12.4 g. ofmonoethylol guanidine was obtained. 30.9 g. of p-toluidine diazonium chloride was then added with stirring to 133 cc;

It isalmost insolubleiin waterzibut" readily: soluble' acetone; denatured ethyl-*alcoliol and dioxane.

Any one of-a number of couplinggcomponentsknown to thoseversed in the art cantbeadmixed with this diazo: compound, such: as: I-na'plithol; the" o-toluidide of 2,3-hydroxymaphthoic" acid, the 2',5i-dimethoxy. anilideof: 2-,3'-hydroxy-naph'- thoic acid, or the 4-chloranilide oi 2,3-hydroxynaphthoic acid. When mixed? with: an alkaline: aqueous alcohol solution of sodium a-naphtholate it showed a very high degree of stability and no formation o't dyestufi'occurrede Coupling took place immediately uponi acidification of this mixture with acetic acid while heatirig to yield a red dye; V v

, EXAMPLE II:-

Anaqueous solution of diethylol guanidinewas prepared by reacting 46'g.'ofmonoetliylol cyan'amide prepared asdescribedabovezand containing 12% water with: 84.5 g. of ethylo'lamine hydrochloride; The reactants wi'eree heated'overa pe- 1*i0d10f 30 minutesito 130 Cnand then at 130 to 140 C. for 10 minutes towyildQLg. oftheidi ethylol guanidine hydrochloridei as alightyellow liquid. Then l'llfi'g. ofthisidiethylol glu'anie dine hydrochloride was dissolved in 100; ccgzof water cooled with v150 g. oftice... Thiszsolutionwas rendered alkaline by the additionidf 5g. of sodium hydroxide and. 26.3 g; of" sodium'. carbonate to yield th desired solution of diethylol guanidine. 7.7 g. of p-toluidine diazon ium'. chloride was added to the abov diethylol uguanldinei solution and'the' mixture stirredio'r' anihour. A brown somewhat sticky material separated and wasfih tered off and dried at-room temperature toJyieId a b'rown soft material.

This diazo compound haslthe following probable formula-z onzciaon l E V a l nioon y l r N-cmcnion It is sparinglysolublein watr but-readily soluble'in acetone,- denatured ethyl alcohol and dioxane. When mixed with an alkaline. solution of sodium a-n'aphthclate it was stabl at room temperature butshowed some couplingupon heating to 80 C. Coupling takes place readily upon acidification of the mixture with aceticacid and heating as the formation 011a. definite red azo matmsmrcaws;

A reactive ethylene oxide ring and a corresponding substituent in the ethylene oxide ring. Thus instead of ethylene oxide, one or more mol. of glycidol, propylene oxide, isopropylene oxide,

butylerie-oxidey isobutylene oxide, etc. etc., can

be usediniorder to render th stabilized diazo compdundwater soluble. A number of such compounds are describedin the copending application's'Serial Numbers 289,398 and 289,400 of Walter P. Ericks';

It is to be particularly noted that although for. ease of description, the aromatic amine chosen in tneiexammes illustrating specific embodiments of the invention p-toluidine} various other stable diazo compounds can be prepared from practically any ice color diazo component; Thus other.tyiiic'al' aminesiwhich can be diazotized and reacted: with. the stabilizing components. include in addition to p-toluidine, iamonenumerousiotners familiar. tothose versed in the art; aniline as well as'honiologues of aniline, namely; 2,4-di- Inethylanili'ne. Where stillfdtlier' cblor'va'riations' are desired, the halogenderivat ves ofaniline may be used, such as the monochlor'oanilir'ies', dichloranilinesi anilines substitutedby hydrocarhon radicals, such as alkyl, alkoxy'ra'di'ca'l's', for' example methyl; ethyl, et'c., metho'xy, ethoxy; or the lilie; or anilines substituted'by nit'ro radicals, acyl derivativesthereof, and the like;

Similarly, although l-naphthol is give'n'a'sthe most frequently used coupling" component for. tlie'dye' mixture incorporating the specific stabilized diazo' com ounds; various other ,na h'- thol's; such as. n'aphthol" AS, toluidi'des, pyre zolones, coupling? aryiiu'es, particularly arylide's' of 2,3 hydroxy-naphthoic acid, otherhydroiiy or ar'nino-naphtlioio acid, carbazble-carlzvoxyl'ic' acid, hydroxy-anthracene carboxylic acid; anthraquinone carboxylic acid, the anilide of 2,3- hydroxy-naphthoicacid, or the like, may be used as coupling components.

This case is a division ofour co-pending applic'ati'on; Serial N6; 369,806, file'dDe'c; 12,,1940.

It'iis to be understoodtliat'theexamples, here in given are merely illustrative and not lirnit'a tive embodiments of this invention which is t'o be. construed broadly and limited solely as defihe'd by the" scope ofthe' appended" claims.

we claim:

11 A stabilized. 'dia'z'o' compoundhavmg the gem eral formula:

in Ris the nucleus of ani c'e colordiazo component offthe: benzene series; and X is .a} saturated aliphatic radical containing, at leastwetnessstems.-

3. A stabilized diazo compound having the 5. A stabilized diazo compound having the formula: formula:

i i f f- 5 HaC- 3N=NNCNCH:CH:OH NH 1% in which R is the nucleus of an ice color diazo I component of the benzene series 6. A stabilized diazo compound having the 4. A stabilized diazo compound having the formula: formula: 10 01120112011 x011 H H ll NE in which R is the nucleus of an ice color diazo 15 component of the benzene series and X is a PAUL P. MCCLELLAN.

saturated aliphatic radical containing at least WALTER P. ERICKS. two carbon atoms. 

